Abstract
Reacting neutral Pt(ii) hydroxo compounds (NN)Pt(R)(OH) (R = OH, Ph, and Me, NN = bulky terphenyl diimine) with silver bis(trifluromethanesulfonyl)imide produces new hydroxo complexes with the silver binding through the Pt-OH bonds as determined by (195)Pt NMR and X-ray analysis (R = OH). These complexes were found to activate the aromatic C-D bonds of C6D6 at significantly enhanced rates relative to the silver free hydroxo complexes. Mechanistic studies for R = Ph are consistent with a homogeneous pathway that is bimolecular (ΔH(‡) = 17(2) kcal mol(-1) and ΔS(‡) = -25(6) e.u. and ΔG = 10(2) kcal mol(-1)), first order in [Pt] and substrate.
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